Fungicidal 2-methoximinocarboxylic esters

ABSTRACT

Fungicidal new 2-methoximinocarboxylic esters of the general formula (I) ##STR1## in which Ar represents one of the radicals ##STR2## A represents one of the radicals --CH 2  --; ##STR3## where Y represents one of the radicals ##STR4##  --SO 2  --CH 2  --; --O--; --CH═CH-- or --CH 2  --CH 2  --, 
     n represents the number 0 or 1, 
     R represents alkyl, halogenoalkyl, alkenyl, halogenoalkenyl, or represents optionally substituted cycloalkyl, or represents optionally substituted aryl or represents optionally substituted heteroaryl, and, moreover, in the event that n is 0, also represents halogen, and 
     X 1 , X 2 , X 3  and X 4  independently of one another in each case represent hydrogen, halogen, hydroxyl or methoxy, but where, in the event that X 2  represents bromine, X 3  does not simultaneously represent hydroxyl or methoxy.

The invention relates to new 2-methoximinocarboxylic esters, to severalprocesses for their preparation, and to their use as pesticides.

It is known that certain carboxylic esters such as, for example, thecompound methyl 3-methoxy-2-(2-methylphenyl)-acrylate, have fungicidalactivity (compare, for example, European Patent 178,826).

However, the activity of these previously known compounds is notentirely satisfactory in all fields of application, in particular whenlow amounts and concentrations are used.

Furthermore, certain 2-methoximinocarboxylic esters are known (compare,for example, Tetrahedron Lett. 23, 3699-3702 [1982]; Tetrahedron Lett.22, 3247-3248 [1981]; Austral. J. Chem. 34, 765-768 [1981]; TetrahedronLett. 21, 2277-2280 [1980]; J. Chem. Soc., Perkin Trans. 1, 1975,2340-2348; Experientia 31, 756-757 [1975]; J. Chem. Soc., Perkin Trans.1, 1972, 18-24). Nothing has been known to date about an activity ofthese previously known compounds as pesticides.

New 2-methoximinocarboxylic esters have been found, of the generalformula (I), ##STR5## in which Ar represents one of the radicals##STR6## A represents one of the radicals --CH₂ --; ##STR7## where Yrepresents one of the radicals ##STR8## --SO₂ --CH₂ --; --O--; --CH═CH--or --CH₂ --CH₂ --,

n represents the number 0 or 1,

R represents alkyl, halogenoalkyl, alkenyl, halogenoalkenyl, orrepresents optionally substituted cycloalkyl, or represents optionallysubstituted aryl or represents optionally substituted heteroaryl, and,moreover, in the event that n is 0, also represents halogen, and

X¹, X², X³ and X⁴ independently of one another in each case representhydrogen, halogen, hydroxyl or methoxy, but where, in the event that X²represents bromine, X³ does not simultaneously represent hydroxyl ormethoxy.

The compounds of the formula (I) can be in the form of geometric isomersor mixtures of isomers of various compositions. The invention claims thepure isomers and also the mixtures of isomers.

Furthermore, it has been found that the new 2-methoximinocarboxylicesters of the general formula (I), ##STR9## in which Ar represents oneof the radicals ##STR10## A represents one of the radicals --CH₂ --;##STR11## where Y represents one of the radicals ##STR12## --SO₂ --CH₂--; --O--; --CH═CH-- or --CH₂ --CH₂ --,

n represents the number 0 or 1,

R represents alkyl, halogenoalkyl, alkenyl, halogenoalkenyl, orrepresents optionally substituted cycloalkyl, or represents optionallysubstituted aryl or represents optionally substituted heteroaryl, and,moreover, in the event that n is 0, also represents halogen, and

X¹, X², X³ and X⁴ independently of one another in each case representhydrogen, halogen, hydroxyl or methoxy, but where, in the event that X²represents bromine, X³ does not simultaneously represent hydroxyl ormethoxy,

are obtained by one of the processes described below:

(a) 2-methoximinocarboxylic esters of the formula (Ia), ##STR13## inwhich R¹ represents hydrogen or methyl and

Ar has the abovementioned meaning,

are obtained when acrylic ester derivatives of the formula (II),##STR14## in which R¹ and Ar have the abovementioned meanings,

are reacted with an acid addition salt of O-methylhydroxylamine, ifappropriate in the presence of a diluent and if appropriate in thepresence of a reaction auxiliary;

(b) 2-methoximinocarboxylic esters of the formula (Ib), ##STR15## inwhich Ar has the abovementioned meaning,

are obtained when, in a first step, aromatic amines of the formula(III),

    Ar--NH--CH.sub.3                                           (III)

in which

Ar has the abovementioned meaning,

are first reacted with methyl 2-chloro-2-hydroximinoacetate of theformula (IV) ##STR16## if appropriate in the presence of a diluent andif appropriate in the presence of an acid-binding agent, and, in asecond step, the product is subsequently methylated on the hydroximinogroup using a methylation agent, if appropriate in the presence of anacid-binding agent;

(c) 2-methoximinocarboxylic esters of the formula (Ic), ##STR17## inwhich R1 represents hydrogen or methyl and

Ar¹ represents one of the radicals ##STR18## Y¹ in each case representsone of the radicals ##STR19## X¹, X², X³, X⁴ and R have theabovementioned meanings, are alternatively also obtained whensubstituted phenol or aniline derivatives of the formula (V), ##STR20##in which R¹ represents hydrogen or methyl and

Ar² represents one of the radicals ##STR21## Z in each case representshydroxyl, amino or N-methylamino and X¹, X², X³ and X⁴ have theabovementioned meanings,

are acylated with acid chlorides of the formula (VI), ##STR22## in whichR has the abovementioned meaning,

if appropriate in the presence of a diluent and if appropriate in thepresence of an acid-binding agent.

Finally, it has been found that the new 2-methoximinocarboxylic estersof the general formula (I) have a highly pronounced activity againstpests.

Surprisingly, the 2-methoximinocarboxylic esters of the general formula(I) according to the invention show considerably better fungicidalactivity than the carboxylic esters known from the prior art, such as,for example, the compound methyl 3-methoxy-2-(2-methylphenyl)-acrylate,which are similar compounds chemically and from the point of view oftheir action.

Formula (I) provides a general definition of the 2-methoximinocarboxylicesters according to the invention.

In the definitions mentioned under the general formula (I),

R preferably represents straight-chain or branched alkyl having 1 to 8carbon atoms, straight-chain or branched halogenoalkyl having 1 to 8carbon atoms and 1 to 9 identical or different halogen atoms,straight-chain or branched alkenyl having 2 to 8 carbon atoms,straight-chain or branched halogenoalkenyl having 2 to 8 carbon atomsand 1 to 9 identical or different halogen atoms, or representscycloalkyl which has 3 to 7 carbon atoms and which is optionallymonosubstituted or polysubstituted by identical or differentsubstituents from the series comprising halogen and/or straight-chain orbranched alkyl having 1 to 6 carbon atoms, or represents heteroarylwhich has 2 to 9 carbon atoms and 1 to 5 identical or different heteroatoms--in particular nitrogen, oxygen and/or sulphur--and which isoptionally monosubstituted or polysubstituted by identical or differentsubstituents, suitable heteroaryl substituents in each case being:halogen and in each case straight-chain or branched alkyl or alkoxy eachof which has 1 to 6 carbon atoms; or

R furthermore preferably represents aryl which has 6 to 10 carbon atomsand which is optionally monosubstituted or polysubstituted by identicalor different substituents, suitable aryl substituents being: halogen,cyano, nitro, in each case straight-chain or branched alkyl, alkoxy,alkylthio, alkylsulphinyl or alkylsulphonyl each of which has 1 to 6carbon atoms, in each case straight-chain or branched alkenyl, alkynyl,alkenyloxy, alkynyloxy, alkenylthio or alkynylthio each of which has 2to 6 carbon atoms, in each case straight-chain or branchedhalogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinyland halogenoalkylsulphonyl each of which has 1 to 6 carbon atoms and 1to 13 identical or different halogen atoms, in each case straight-chainor branched halogenoalkenyl, halogenoalkynyl, halogenoalkenyloxy,halogenoalkynyloxy, halogenoalkenylthio or halogenoalkynylthio each ofwhich has 2 to 6 carbon atoms and 1 to 9 identical or different halogenatoms, in each case straight-chain or branched alkylcarbonyl,alkoxycarbonyl, alkylcarbonyloxy, alkylcarbonylamino,alkylcarbonyl-(N-alkyl)-amino, aminocarbonyl, N-alkyl-aminocarbonyl,N,N-dialkylaminocarbonyl or alkoximinoalkyl each of which has 1 to 6carbon atoms in the individual alkyl moieties, and aryl, aryloxy,arylthio, arylcarbonyl, arylcarbonyloxy, arylcarbonylamino,arylcarbonyl-(N-alkyl)amino, arylaminocarbonyl,N-aryl-N-alkylaminocarbonyl, arylalkyl or arylalkenyl each of which has6 to 10 carbon atoms in the aryl moiety and, if appropriate, up to 6carbon atoms in the individual alkyl or alkenyl moieties and each ofwhich is optionally monosubstituted or polysubstituted by identical ordifferent substituents, suitable substituents in the individual arylmoieties in each case being: halogen, cyano, nitro, in each casestraight-chain or branched alkyl, alkoxy, alkylthio, alkylsulphinyl, oralkylsulphonyl each of which has 1 to 6 carbon atoms, in each casestraight-chain or branched alkenyl, alkynyl, alkenyloxy, alkynyloxy,alkenylthio or alkynylthio each of which has 2 to 6 carbon atoms, ineach case straight-chain or branched halogenoalkyl, halogenoalkoxy,halogenoalkylthio, halogenoalkylsulphinyl and halogenoalkylsulphonyleach of which has 1 to 6 carbon atoms and 1 to 13 identical or differenthalogen atoms, in each case straight-chain or branched halogenoalkenyl,halogenoalkynyl, halogenoalkenyloxy, halogenoalkynyloxy,halogenoalkenylthio or halogenoalkynylthio each of which has 2 to 6carbon atoms and 2 to 9 identical or different halogen atoms, in eachcase straight-chain or branched alkylcarbonyl, alkoxycarbonyl,alkylcarbonyloxy, alkylcarbonylamino, alkylcarbonyl-(N-alkyl)-amino,aminocarbonyl, N-alkyl-aminocarbonyl, N,N-dialkylaminocarbonyl oralkoximinoalkyl each of which has 1 to 6 carbon atoms in the individualalkyl moieties, and aryl, aryloxy, arylthio, arylcarbonyl,arylcarbonyloxy, arylcarbonylamino, arylcarbonyl-(N-alkyl)amino,arylaminocarbonyl, N-aryl-N-alkylaminocarbonyl, arylalkyl or arylalkenyleach of which has 6 to 10 carbon atoms in the aryl moiety and ifappropriate up to 6 carbon atoms in the individual alkyl or alkenylmoieties and each of which is optionally monosubstituted orpolysubstituted by identical or different substituents, suitablesubstituents in the individual aryl moieties in each case being: halogenand in each case straight-chain or branched alkyl or alkoxy each ofwhich has 1 to 6 carbon atoms; in the event that n is 0, R furthermorepreferably also represents fluorine, chlorine, bromine or iodine.

In the definitions mentioned under the general formula (I),

R particularly preferably represents straight-chain or branched alkylhaving 1 to 6 carbon atoms, straight-chain or branched halogenoalkylhaving 1 to 6 carbon atoms and 1 to 9 identical or different halogenatoms, straight-chain or branched alkenyl having 2 to 6 carbon atoms,straight-chain or branched halogenoalkenyl having 2 to 6 carbon atomsand 1 to 9 identical or different halogen atoms, cycloalkyl which has 3to 7 carbon atoms and which is optionally monosubstituted topentasubstituted by identical or different substituents from the seriescomprising straight-chain or branched alkyl having 1 to 4 carbon atomsand/or halogen, or heteroaryl which has 2 to 9 carbon atoms and 1 to 4identical or different hetero atoms--in particular nitrogen, oxygenand/or sulphur--and which is optionally monosubstituted totrisubstituted by identical or different substituents, suitableheteroaryl substituents in each case being: fluorine, chlorine, bromineand in each case straight-chain or branched alkyl or alkoxy each ofwhich has 1 to 4 carbon atoms; or

R moreover particularly preferably represents aryl which has 6 or 10carbon atoms and which is optionally monosubstituted to pentasubstitutedby identical or different substituents, suitable aryl substituents ineach case being: fluorine, chlorine, bromine, cyano, nitro, in each casestraight-chain or branched alkyl, alkoxy, alkylthio, alkylsulphinyl oralkylsulphonyl each of which has 1 to 4 carbon atoms, in each casestraight-chain or branched alkenyl, alkynyl, alkenyloxy, alkynyloxy,alkenylthio or alkynylthio each of which has 2 to 4 carbon atoms, ineach case straight-chain or branched halogenoalkyl, halogenoalkoxy,halogenoalkylthio, halogenoalkylsulphinyl and halogenoalkylsulphonyleach of which has 1 to 4 carbon atoms and 1 to 9 identical or differenthalogen atoms, in each case straight-chain or branched halogenoalkenyl,halogenoalkynyl, halogenoalkenyloxy, halogenoalkynyloxy,halogenoalkenylthio or halogenoalkynylthio each of which has 2 to 4carbon atoms and 1 to 7 identical or different halogen atoms, in eachcase straight-chain or branched alkylcarbonyl, alkoxycarbonyl,alkylcarbonyloxy, alkylcarbonylamino, alkylcarbonyl-(N-alkyl)-amino,aminocarbonyl, N-alkyl-aminocarbonyl, N,N-dialkylaminocarbonyl oralkoximinoalkyl each of which has 1 to 4 carbon atoms in the individualalkyl moieties, and aryl, aryloxy, arylthio, arylcarbonyl,arylcarbonyloxy, arylcarbonylamino, arylcarbonyl-(N-alkyl)amino,arylaminocarbonyl, N-aryl-N-alkylaminocarbonyl, arylalkyl or arylalkenyleach of which has 6 to 10 carbon atoms in the aryl moiety and ifappropriate up to 4 carbon atoms in the individual alkyl or alkenylmoieties and each of which is optionally monosubstituted orpolysubstituted by identical or different substituents, suitablesubstituents in the individual aryl moieties in each case being:fluorine, chlorine, bromine, cyano, nitro, in each case straight-chainor branched alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyleach of which has 1 to 4 carbon atoms, in each case straight-chain orbranched alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio oralkynylthio each of which has 2 to 4 carbon atoms, in each casestraight-chain or branched halogenoalkyl, halogenoalkoxy,halogenoalkylthio, halogenoalkylsulphinyl and halogenoalkylsulphonyleach of which has 1 to 4 carbon atoms and 1 to 9 identical or differenthalogen atoms, in each case straight-chain or branched halogenoalkenyl,halogenoalkynyl, halogenoalkenyloxy, halogenoalkynyloxy,halogenoalkenylthio or halogenoalkynylthio each of which has 2 to 4carbon atoms and 1 to 7 identical or different halogen atoms, in eachcase straight-chain or branched alkylcarbonyl, alkoxycarbonyl,alkylcarbonyloxy, alkylcarbonylamino, alkylcarbonyl-(N-alkyl)-amino,aminocarbonyl, N-alkyl-aminocarbonyl, N,N-dialkylaminocarbonyl oralkoximinoalkyl each of which has 1 to 4 carbon atoms in the individualalkyl moieties, and aryl, aryloxy, arylthio, arylcarbonyl,arylcarbonyloxy, arylcarbonylamino, arylcarbonyl-(N-alkyl)amino,arylaminocarbonyl, N-aryl-N-alkylaminocarbonyl, arylalkyl or arylalkenyleach of which has 6 to 10 carbon atoms in the aryl moiety and ifappropriate up to 4 carbon atoms in the individual alkyl or alkenylmoieties and each of which is optionally monosubstituted orpolysubstituted by identical or different substituents, suitablesubstituents in the individual aryl moieties in each case being:fluorine, chlorine, bromine and in each case straight-chain or branchedalkyl or alkoxy each of which has 1 to 4 carbon atoms; or in the eventthat n is 0, R furthermore particularly preferably also representschlorine or bromine.

Moreover, X¹, X², X³ and X⁴ independently of one another in each casepreferably represent hydrogen, fluorine, chlorine, bromine, iodine,hydroxyl or methoxy, but where, in the event that X² represents bromine,X³ does not simultaneously represent hydroxyl or methoxy.

In particular, X¹, X², X³ and X⁴ independently of one another in eachcase represent hydrogen, chlorine, bromine, hydroxyl or methoxy, butwhere, in the event that X² represents bromine, X³ does notsimultaneously represent hydroxyl or methoxy.

In the definitions listed under the general formula (I), Ar preferablyrepresents the radical ##STR23## where R, Y, n, X¹, X², X³ and X⁴ canhave the meanings indicated above.

If, for example, methyl2-acetamido-3-[3-(4-chlorophenyl)-phenyl]-acrylate andO-methylhydroxylamine hydrochloride are used as starting substances, thecourse of the reaction of process (a) according to the invention can beoutlined by the following equation: ##STR24##

If, for example, methyl 2-chloro-2-hydroximinoacetate andN-methyl-3-trifluoromethylaniline are used as starting substances anddimethyl sulphate as methylating agent, the course of the reaction ofprocess (b) according to the invention can be outlined by the followingequation: ##STR25##

If, for example, methyl 3-(3-hydroxyphenyl)-2-methoximino-propionate and3-chlorobenzoyl chloride are used as starting substances, the course ofthe reaction of process (c) according to the invention can be outlinedby the following equation: ##STR26##

Formula (II) provides a general definition of the acrylic esterderivatives required as starting substances for carrying out process (a)according to the invention. In this formula (II), Ar preferablyrepresents those radicals which have already been mentioned inconnection with the description of the substances of the formula (I)according to the invention as being preferred for these substituents.

R¹ preferably represents hydrogen or methyl. The acrylic esterderivatives of the formula (II) are known (compare, for example,Synthesis 1989, 414-418; Jpn. Kokai Tokkyo Koho JP 61218558; J. LabelledComp. Radiopharm. 21, 263-284 [1984]; Liebigs Ann. Chem. 1984.1205-1215) or can be obtained in analogy to known processes (compare,for example, Organic Reactions Vol. III, Azlactones p. 198-239), forexample when aromatic aldehydes or ketones of the formula (VII),##STR27## in which R¹ and Ar have the abovementioned meanings,

are reacted with N-acetylglycine in the presence of acetic anhydride andsodium acetate and if appropriate in the presence of acetic acid attemperatures between 20° C. and 160° C. and then, in a second step, theresulting azlactones of the formula (VIII), ##STR28## in which R¹ and Arhave the abovementioned meanings,

are reacted in methanol, if appropriate in the presence of a base suchas, for example, sodium hydroxide or sodium methylate, at temperaturesbetween 0° C. and 50° C.

Aromatic aldehydes and ketones of the formula (VII) are generally knowncompounds of organic chemistry or can be obtained in analogy togenerally known processes.

Formula (III) provides a general definition of the aromatic aminesrequired as starting substances for carrying out process (b) accordingto the invention. In this formula (III), Ar preferably represents thoseradicals which have already been mentioned in connection with thedescription of the substances of the formula (I) according to theinvention as being preferred for these substituents.

The aromatic amines of the formula (III) are likewise generally knowncompounds of organic chemistry.

Methyl 2-chloro-2-hydroximino-acetate, of the formula (IV), which isfurthermore required as a starting compound for carrying out process (b)according to the invention, is likewise known (compare DE 1,963,061;U.S. Pat. No. 3,584,032).

Formula (V) provides a general definition of the substituted phenol andaniline derivatives required as starting substances for carrying outprocess (c) according to the invention. In this formula (V), R¹preferably represents hydrogen or methyl and Ar² represents one of theradicals ##STR29## Z in each case represents hydroxyl, amino orN-methylamino and X¹, X², X³ and X⁴ preferably represent those radicalswhich have already been mentioned in connection with the description ofthe substances of the formula (I) according to the invention as beingpreferred for these substituents.

The substituted phenol and aniline derivatives of the formula (V) werehitherto unknown and are likewise a subject of the invention.

They are obtained when azlactones of the formula (IX), ##STR30## inwhich R¹ has the abovementioned meaning and

Ar³ represents one of the radicals ##STR31## Z¹ in each case representsoxygen, an NH group or an ##STR32## X¹, X², X³ and X⁴ have theabovementioned meanings, are reacted with methanol in the presence of abase such as, for example, sodium hydroxide and subsequently in thepresence of an acid such as, for example, hydrochloric acid, attemperatures between 0° C. and 50° C., and the resulting acrylic esterderivatives of the formula (X), ##STR33## in which R¹ has theabovementioned meaning and

Ar² represents one of the radicals ##STR34## Z in each case representshydroxyl, amino or N-methylamino and X¹, X², X³ and X⁴ have theabovementioned meanings,

are subsequently reacted with an acid addition salt ofO-methylhydroxylamine such as, for example, O-methylhydroxylaminehydrochloride, if appropriate in the presence of a diluent such as, forexample, methanol and if appropriate in the presence of a reactionauxiliary such as, for example, sulphuric acid, in analogy to theprocedure of process (a) according to the invention at temperaturesbetween 20° C. and 60° C.

Azlactones of the formula (IX) are known (compare, for example, TakedaKenkyushoho 43, 53-76 [1984]; Izv. Akad. Nauk SSSR, Ser. Khim. 1984,1090-1094; Izv. Akad. Nauk SSSR, Ser. Khim. 1980, 823-829; TetrahedronLett. 1979, 737-740; Bull. Soc. Chim. Belg., 83 (3/4), 117-132 [1974];DE 2,243,665; BE 715,588; ZA 6803 083) or can be obtained in analogy toknown processes (compare, for example, Organic Reactions Vol. III,Azlactones, p. 108-239).

Formula (VI) provides a general definition of the acid chloridesfurthermore required as starting substances for carrying out process (c)according to the invention. In this formula (VI), R preferablyrepresents those radicals which have already been mentioned inconnection with the description of the substances of the formula (I)according to the invention as being preferred for this substituent

The acid chlorides (VI) are generally known compounds of organicchemistry.

Suitable diluents for carrying out process (a) according to theinvention are polar organic solvents or aqueous systems. Diluents whichare particularly preferably used are alcohols such as, for example,methanol, ethanol or propanol, their mixtures with water, or pure water.

Suitable reaction auxiliaries for carrying out process (a) according tothe invention are strong mineral acids such as hydrochloric acid,hydrobromic acid or sulphuric acid.

When carrying out process (a) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between 0° C. and 100° C.,preferably at temperatures between 20° C. and 60° C.

For carrying out process (a) according to the invention, 1.0 to 3.0moles, preferably 1.0 to 1.5 moles, of O-methylhydroxylamine and, ifappropriate, 1.0 to 3.0 moles, preferably 1.0 to 1.5 moles, of reactionauxiliary are generally employed per mole of acrylic ester derivative ofthe formula (II). The reaction is carried out and the reaction productsare worked up and isolated by generally customary methods (compare alsothe preparation examples).

Suitable diluents for carrying out process (b) according to theinvention, both for step 1 and for step 2, are inert organic solvents.These include, in particular, aliphatic, alicyclic or aromatic,optionally halogenated hydrocarbons such as, for example, benzine,benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane,cyclohexane, dichloromethane, tetrachloroethane, chloroform, carbontetrachloride, ethers such as diethyl ether, dioxane, tetrahydrofuran orethylene glycol dimethyl ether or ethylene glycol diethyl ether, ketonessuch as acetone or butanone, nitriles such as acetonitrile orpropionitrile, amides such as dimethylformamide,dimethylacetamide,N-methylformanilide,N-methylpyrrolidone orhexamethylphosphoric triamide, esters such as ethyl acetate, orsulphoxides such as dimethyl sulphoxide.

Process (b) according to the invention is preferably carried out in thepresence of a suitable acid-binding agent. Suitable acid-binding agents,both for step 1 and also for step 2, are all inorganic and organic baseswhich can customarily be used. The following are preferably used: thehydrides, hydroxides, amides, alcoholates, carbonates or hydrogencarbonates of alkali metals such as, for example, sodium hydride, sodiumamide, sodium hydroxide, sodium methylate, sodium ethylate, potassiumt-butylate, sodium carbonate or sodium hydrogen carbonate, and alsotertiary amines such as, for example, triethylamine,N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine,diazabicyclooctane (DABCO), diazabicyclononene (DBN) ordiazabicycloundecene (DBU).

When carrying out step 1 of process (b) according to the invention, thereaction temperatures can be varied in a substantial range. In general,the process is carried out at temperatures between -20° C. and 100° C.,preferably at temperatures between 0° C. and 80° C.

For carrying out step 1 of process (b) according to the invention, 1.0to 1.5 moles, preferably 1.0 to 1.2 moles, of methyl2-chloro-2-hydroximinoacetate, of the formula (IV), and, if appropriate,1.0 to 1.5 moles, preferably 1.0 to 1.2 moles, of acid-binding agent aregenerally employed per mole of aromatic amine of the formula (III). Thereaction is carried out and the reaction products are worked up andisolated by generally customary methods.

Suitable methylating agents for carrying out step 2 of process (b)according to the invention are all the methylating agents which cancustomarily be used. The following are preferably used: dimethylsulphate, methyl p-toluenesulphonate, methyl iodide or methyl bromide.Dimethyl sulphate is particularly suitable.

When carrying out step 2 of process (b) according to the invention, thereaction temperatures can be varied within a substantial range. Ingeneral, the process is carried out at temperatures between -20° C. and100° C., preferably at temperatures between 0° C. and 80° C.

For carrying out step 2 of process (b) according to the invention, 1.0to 1.5 moles, preferably 1.0 to 1.2 moles, of methylating agents and, ifappropriate, 1.0 to 1.5 moles, preferably 1.0 to 1.2 moles, ofacid-binding agent are generally employed per mole of hydroximinostarting compound. The reaction is carried out and the reaction productsare worked up and isolated by generally customary methods (compare alsothe preparation examples).

Suitable diluents for carrying out process (c) according to theinvention are inert organic solvents. These include, in particular,aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbonssuch as, for example, benzine, benzene, toluene, xylene, chlorobenzene,petroleum ether, hexane, cyclohexane, dichloromethane, chloroform,carbon tetrachloride, ethers such as diethyl ether, dioxane,tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycoldiethyl ether, ketones such as acetone or butanone, nitriles such asacetonitrile or propionitrile, amides such as dimethylformamide,dimethylacetamide,N-methylformanilide,N-methylpyrrolidone orhexamethylphosphoric triamide, esters such as ethyl acetate, orsulphoxides such as dimethyl sulphoxide.

Process (c) according to the invention is preferably carried out in thepresence of a suitable acid-binding agent. Suitable acid-binding agentsare all the customary inorganic or organic bases. These include, forexample, alkali metal hydroxides such as sodium hydroxide or potassiumhydroxide, alkali metal carbonates such as sodium carbonate, potassiumcarbonate or sodium hydrogen carbonate, and also tertiary amines such astriethylamine, N,N-dimethylaniline,pyridine,N,N-dimethylaminopyridine,diazabicyclooctane (DABCO), diazabicyclononene (DBN) ordiazabicycloundecene (DBU).

When carrying out process (c) according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between -20° C. and 100° C.,preferably at temperatures between 0° C. and 60° C.

For carrying out process (c) according to the invention, 1.0 to 1.5moles, preferably 1.0 to 1.2 moles, of acid chloride of the formula (VI)and, if appropriate, 1.0 to 1.5 moles, preferably 1.0 to 1.2 moles, ofacid-binding agent are generally employed per mole of phenol or anilinederivative of the formula (V).

The reaction is carried out and the reaction products are worked up andisolated by generally customary methods (compare also the preparationexamples).

The active compounds according to the invention have a powerful actionagainst pests and can be employed in practice for combating undesiredharmful organisms. The active substances are suitable for use as plantprotection agents, in particular as fungicides.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Some causative organisms of fungal diseases which come under the genericnames listed above may be mentioned as examples, but not by way oflimitation:

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonosporahumuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Peronospora species, such as, for example, Peronospora pisi or P.brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P.graminea (conidia form: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus(conidia form: Drechslera, syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilagoavenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae and

Pseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

In this context, the active compounds according to the invention can beemployed with particularly good success for combating cereal diseasessuch as, for example, against the causative organism of powdery mildewof cereals (Erysiphe graminis) on barley or wheat, or against thecausative organism of net blotch disease of barley (Pyrenophora teres)or against the causative organism of brown spot (Cochliobolus sativus)on barley or wheat, or against the causative organism of brown blotch ofwheat (Leptosphaeria nodorum) or against the causative organism of snowmold of cereals (Fusarium nivale), or for combating rice diseases suchas, for example, against the causative organism of rice blast disease(Pyricularia oryzae), or for combating diseases in fruit growing andvegetable growing, such as, for example, against the causative organismof apple scab (Venturia inaequalis).

Depending on their particular physical and/or chemical properties, theactive compounds can be converted into the customary formulations, suchas solutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols, very fine capsules in polymeric substances and in coatingcompositions for seed, as well as ULV cold-mist and warm-mistformulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents and/or foam-forming agents. In the case of the use of water as anextender, organic solvents can, for example, also be used as auxiliarysolvents. As liquid solvents, there are suitable in the main: aromatics,such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics orchlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at ambient temperature andunder atmospheric pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide; as solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly-disperse silica, alumina and silicates; assolid carriers for granules there are suitable: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,corn cobs and tobacco stalks; as emulsifying and/or foam-forming agentsthere are suitable: for example non-ionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as albumin hydrolysis products; asdispersing agents there are suitable: for example ligninsulphite wasteliquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in theformulations as a mixture with other known active compounds, such asfungicides, insecticides, acaricides and herbicides, as well as inmixtures with fertilisers and growth regulators.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, suspensions, wettable powders, pastes, soluble powders, dustsand granules. They are used in the customary manner, for example bywatering, spraying, atomizing, scattering, dusting, foaming, brushing onand the like. It is furthermore possible to apply the active compoundsby the ultra-low volume method or to inject the active compoundformulation or the active compound itself into the soil. The seeds ofthe plants can also be treated.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001%. In the treatment of seed, amounts of active compound of 0.001 to50 g per kilogram of seed, preferably 0.01 to 10 g, are generallyrequired.

In the treatment of soil, active compound concentrations of 0.00001 to0.1% by weight, preferably 0.0001 to 0.02% by weight, are required atthe place of action.

PREPARATION EXAMPLES EXAMPLE 1 ##STR35##

To a suspension of 130 g (0.395 mol) of methyl2-acetamido-3-[3-(4-chlorophenyl)-phenyl]-acrylate in 500 ml of methanolthere are added 36 g (0.435 mol) of O-methylhydroxylamine hydrochlorideand 43.5 ml (0.435 mol) of concentrated hydrochloric acid, the mixtureis refluxed for 38 hours and then concentrated in vacuo, the residue istaken up in 1 l of dichloromethane, the mixture is washed three timesusing 500 ml of water each time and dried over sodium sulphate, thesolvent is removed in vacuo, and the residue is purified bychromatography on silica gel (eluent: dichloromethane).

104.2 g (83% of theory) of methyl3-[3-(4-chlorophenyl)-phenyl]-2-methoximinopropionate are obtained as anoil of refractive index n_(D) ²³ of 1.5919.

Preparation of the starting compound EXAMPLE II-1 ##STR36##

To a suspension of 130 g (0.437 mol) of4-[3-(4-chlorophenyl)-benzylidene]-2-methyl-1,3-oxazolin-5-one in 500 mlof methanol there are added 1.7 ml (0.022 mol) of 50 percent strengthaqueous sodium hydroxide solution, and the mixture is then stirred for18 hours at 20° C. For working up, the solid which has precipitated isfiltered off with suction, washed with 200 ml of diethyl ether anddried.

130 g (90% of theory) of methyl2-acetamido-3-[3-(4-chlorophenyl)-phenyl]-acrylate of melting point 168°C. are obtained.

EXAMPLE VIII-1 ##STR37##

To a suspension of 179 g (0.827 mol) of 3-(4-chlorophenyl)-benzaldehydein 1 l of acetic anhydride there are added 117.1 g (1 mol) ofN-acetylglycine and 82 g (1 mol) of sodium acetate, and the mixture isstirred for 18 hours at 130° C. For working up, the solvent is distilledoff under a water pump vacuum, the residue is taken up in 2 l ofdichloromethane, the mixture is washed three times using 1 l of watereach time, dried over sodium sulphate and concentrated in vacuo. Theresidue is crystallized by stirring with 300 ml of acetonitrile,filtered off with suction and dried.

115.9 g (47% of theory) of4-[3-(4-chlorophenyl)-benzylidene]-2-methyl-1,3-oxazolin-5-one ofmelting point 150° C. are obtained.

EXAMPLE 2 ##STR38##

To 0.5 g (0.0018 mol) of methyl2-(hydroximino)-2-[N-methyl-N-(3-trifluoromethylphenyl)-amino]-acetatein 30 ml of tetrahydrofuran there are added 0.3 g (0.0018 mol) ofpotassium carbonate and 0.2 ml (0.0018 mol) of dimethyl sulphate, themixture is stirred for 16 hours at 20° C., the solid which hasprecipitated is then filtered off with suction, the filtrate isconcentrated under a water pump vacuum, and the residue ischromatographed over silica gel (eluent: toluene/ethyl acetate 1:1).

0.5 g (100% of theory) of methyl2-methoximino-2-[N-methyl-N-(3-trifluoromethylphenyl)-amino]-acetate areobtained as an oil.

¹ H-NMR (CDCl₃ /tetramethylsilane): δ=4.12 (3H,s); 3.66 (3H,s); 3.22(3H,s)ppm.

Preparation of the starting compound ##STR39##

To 6.8 g (0.039 mol) of N-methyl-3-trifluoromethylaniline in 50 ml oftoluene there are added 5.4 ml (0.039 mol) of triethylamine andsubsequently at 5° C., dropwise and with stirring, a solution of 5.4 g(0.039 mol) of methyl 2-chloro-2-hydroximino acetate in 17 g of toluene.The mixture is allowed to stand for 16 hours at room temperature, thenwashed twice with 50 ml of water each time, dried over sodium sulphateand concentrated in vacuo and the residue is chromatographed on silicagel (eluent: toluene/ethyl acetate 1:1).

0.5 g (4.6% of theory) of methyl2-hydroximino-2-[N-methyl-N-(3-trifluoromethylphenyl)-amino]-acetate ofmelting point 131° C. are obtained.

EXAMPLE 3 ##STR40##

To 4.4 g (0.02 mol) of methyl3-(3-hydroxyphenyl)-2-methoximinopropionate and 2.8 ml (0.02 mol) oftriethylamine in 20 ml of ethyl acetate there are added dropwise in thecourse of 10 minutes at room temperature 3.5 g (0.02 mol) of3-chlorobenzoyl chloride in 10 ml of ethyl acetate, during which thetemperature of the reaction mixture rises to 30° C. The mixture isstirred for one hour at room temperature and then washed twice using 100ml of water each time, dried over sodium sulphate and concentrated invacuo, and the residue is crystallized by stirring with 20 ml ofn-hexane, filtered off with suction and dried.

5.2 g (72% of theory) of methyl3-[3-(3-chlorobenzoyloxy)-phenyl]-2-methoximinopropionate of meltingpoint 65° C. are obtained.

Preparation of the starting compound EXAMPLE V-1 ##STR41##

To 142.9 g (0.61 mol) of methyl 3-(3-hydroxyphenyl)-2-acetamidoacrylatein 600 ml of methanol there are added 50.6 g (0.61 mol) ofO-methylhydroxylamine hydrochloride and then, dropwise and withstirring, 61 g (0.61 mol) of concentrated sulphuric acid, during whichthe temperature of the reaction mixture rises to 35° C. The mixture isstirred for 30 minutes at room temperature and then refluxed for 18hours. For working up, the solvent is distilled off under a water pumpvacuum, the residue is taken up in 600 ml of dichloromethane, washedtwice with 300 ml of water each time, dried over sodium sulphate andconcentrated in vacuo, and the residue is chromatographed on silica gel(eluent: dichloromethane/methanol 100:2.5) and subsequently crystallizedfrom 150 ml of n-hexane/diisopropyl ether (9:1).

77.9 g (57% of theory) of methyl3-(3-hydroxyphenyl)-2-methoximinopropionate of melting point 75° C. areobtained.

EXAMPLE X-1 ##STR42##

To 124.7 g (0.51 mol) of4-(3-acetoxybenzylidene)-2-methyl-2-oxazolin-5-one (compare DE2,243,665) in 600 ml of methanol there is added 0.44 ml (0.005 mol) of50 percent strength sodium hydroxide solution, the mixture is thenstirred for 3 hours at 65° C., a further 4 ml (0.045 mol) of 50 percentsodium hydroxide solution are added, and the mixture is stirred for 16hours at 20° C. For working up, 5 ml (0.05 mol) of concentratedhydrochloric acid are added, the solvent is distilled off, 500 ml ofwater are added, and the solid which has precipitated is filtered offwith suction.

102.7 g (86% of theory) of methyl3-(3-hydroxyphenyl)-2-acetamidoacrylate of melting point 115° C. areobtained.

The following 2-methoximinocarboxylic esters of the general formula (I)are obtained in a corresponding manner and following the generalpreparation instructions:

    __________________________________________________________________________     ##STR43##                                  (I)                               Example                               Physical                                No.  Ar                          A    properties                              __________________________________________________________________________     4                                                                                  ##STR44##                  CH.sub.2                                                                           m.p.: 55° C.                      5                                                                                  ##STR45##                  CH.sub.2                                                                           n.sub.D.sup.23 : 1.5620                  6                                                                                  ##STR46##                  CH.sub.2                                                                           m.p.: 60° C.                      7                                                                                  ##STR47##                  CH.sub.2                                                                           n.sub.D.sup.23 : 1.5609                  8                                                                                  ##STR48##                  CH.sub.2                                                                           n.sub.D.sup.20 : 1.5822                  9                                                                                  ##STR49##                  CH.sub.2                                                                           n.sub.D.sup.20 : 1.5468                 10                                                                                  ##STR50##                  CH.sub.2                                                                           m.p.: 70° C.                     11                                                                                  ##STR51##                  CH.sub.2                                                                           m.p.: 35° C.                     12                                                                                  ##STR52##                  CH.sub.2                                                                           m.p.: 62° C.                     13                                                                                  ##STR53##                  CH.sub.2                                                                           m.p.: 120° C.                    14                                                                                  ##STR54##                  CH.sub.2                                                                           m.p.: 106° C.                    15                                                                                  ##STR55##                  CH.sub.2                                                                           n.sub.D.sup.20 : 1.5641                 16                                                                                  ##STR56##                  CH.sub.2                                                                           n.sub.D.sup.20 : 1.5682                 17                                                                                  ##STR57##                  CH.sub.2                                                                           n.sub.D.sup.23 : 1.5579                 18                                                                                  ##STR58##                  CH.sub.2                                                                           m.p.: 90° C.                     19                                                                                  ##STR59##                  CH.sub.2                                                                           m.p.: 104° C.                    20                                                                                  ##STR60##                  CH.sub.2                                                                           m.p.: 56° C.                     21                                                                                  ##STR61##                  CH.sub.2                                                                           n.sub.D.sup.20 : 1.6261                 22                                                                                  ##STR62##                  CH.sub.2                                                                           m.p.: 110° C.                    23                                                                                  ##STR63##                  CH.sub.2                                                                           m.p.: 100° C.                    24                                                                                  ##STR64##                  CH.sub.2                                                                           m.p.: 60° C.                     25                                                                                  ##STR65##                  CH.sub.2                                                                           m.p.: 70° C.                     26                                                                                  ##STR66##                  CH.sub.2                                                                           m.p.: 68° C.                     27                                                                                  ##STR67##                  CH.sub.2                                                                           m.p.: 96° C.                     28                                                                                  ##STR68##                  CH.sub.2                                                                           n.sub.D.sup.20 : 1.5592                 29                                                                                  ##STR69##                  CH.sub.2                                                                           n.sub.D.sup.20 : 1.5448                 30                                                                                  ##STR70##                  CH.sub.2                                                                           m.p.: 86° C.                     31                                                                                  ##STR71##                  CH.sub.2                                                                           n.sub.D.sup.20 : 1.5699                 32                                                                                  ##STR72##                  CH.sub.2                                                                           m.p.: 100° C.                    33                                                                                  ##STR73##                                                                                                 ##STR74##                                                                         n.sub.D.sup.20 : 1.5753                 34                                                                                  ##STR75##                  CH.sub.2                                                                           n.sub.D.sup.23 : 1.5261                 35                                                                                  ##STR76##                  CH.sub.2                                                                           m.p.: 60° C.                     36                                                                                  ##STR77##                  CH.sub.2                                                                           n.sub.D.sup.20 : 1.5738                 37                                                                                  ##STR78##                  CH.sub.2                                                                           m.p.: 92° C.                     38                                                                                  ##STR79##                  CH.sub.2                                                                           m.p.: 130° C.                    39                                                                                  ##STR80##                  CH.sub.2                                                                           m.p.: 96° C.                     40                                                                                  ##STR81##                  CH.sub.2                                                                           m.p.: 154°  C.                   41                                                                                  ##STR82##                  CH.sub.2                                                                           m.p. 95° C.                      42                                                                                  ##STR83##                  CH.sub.2                                                                           m.p. 142° C.                     43                                                                                  ##STR84##                  CH.sub.2                                                                           m.p. 58° C.                      44                                                                                  ##STR85##                  CH.sub.2                                                                           m.p. 38° C.                      45                                                                                  ##STR86##                  CH.sub.2                                                                           m.p. 60° C.                      46                                                                                  ##STR87##                  CH.sub.2                                                                           m.p. 178° C.                     47                                                                                  ##STR88##                  CH.sub.2                                                                           m.p. 160° C.                     48                                                                                  ##STR89##                                                                                                 ##STR90##                                                                         m.p. 88°-92° C.           49                                                                                  ##STR91##                  CH.sub.2                                                                           m.p. 78° C.                      50                                                                                  ##STR92##                  CH.sub.2                                                                           n.sub.D.sup.20 : 1.5695                 51                                                                                  ##STR93##                  CH.sub.2                                                                           n.sub.D.sup.20 : 1.5471                 52                                                                                  ##STR94##                  CH.sub.2                                                                           n.sub.D.sup.20 : 1.5363                 53                                                                                  ##STR95##                  CH.sub.2                                                                           n.sub.D.sup.20 : 1.5598                 54                                                                                  ##STR96##                  CH.sub.2                                                                           n.sub.D.sup.20 : 1.5394                 55                                                                                  ##STR97##                  CH.sub.2                                                                           n.sub.D.sup.20 : 1.5214                 56                                                                                  ##STR98##                  CH.sub.2                                                                           n.sub.D.sup.20 : 1.5233                 57                                                                                  ##STR99##                  CH.sub.2                                                                           n.sub.D.sup.20 : 1.5324                 58                                                                                  ##STR100##                 CH.sub.2                                                                           n.sub.D.sup.20 : 1.5711 (mixture of                                           somers)                                 59                                                                                  ##STR101##                 CH.sub.2                                                                           m.p. 120° C.                     60                                                                                  ##STR102##                 CH.sub.2                                                                           m.p. 192° C.                     61                                                                                  ##STR103##                 CH.sub.2                                                                           m.p. 106° C.                     62                                                                                  ##STR104##                                                                                                ##STR105##                                  63                                                                                  ##STR106##                 CH.sub.2                                                                           m.p. 72° C.                      64                                                                                  ##STR107##                 CH.sub.2                                                                           m.p. 68° C.                      65                                                                                  ##STR108##                 CH.sub.2                                                                           m.p. 78° C.                      66                                                                                  ##STR109##                 CH.sub.2                                                                           m.p. 71° C.                      67                                                                                  ##STR110##                 CH.sub.2                                                                           m.p. 50° C.                      68                                                                                  ##STR111##                 CH.sub.2                                                                           n.sub.D.sup.20 : 1.5679                 69                                                                                  ##STR112##                 CH.sub.2                                                                           n.sub.D.sup.20 : 1.5748 (mixture of                                           somers)                                 70                                                                                  ##STR113##                 CH.sub.2                                                                           m.p. 70° C.                      71                                                                                  ##STR114##                 CH.sub.2                                                                           n.sub.D.sup.20 : 1.5978                 72                                                                                  ##STR115##                 CH.sub.2                                                                           m.p. 80° C.                      73                                                                                  ##STR116##                 CH.sub.2                                                                           n.sub.D.sup.20 : 1.5598                 74                                                                                  ##STR117##                 CH.sub.2                                                                           n.sub.D.sup.20 : 1.5807                 75                                                                                  ##STR118##                 CH.sub.2                                                                           m.p. 58° C.                      76                                                                                  ##STR119##                 CH.sub.2                                                                           n.sub.D.sup.20 : 1.5648                 77                                                                                  ##STR120##                 CH.sub.2                                                                           m.p. 70° C.                      78                                                                                  ##STR121##                 CH.sub.2                                                                           n.sub.D.sup.20 : 1.5603 (mixture of                                           somers)                                 79                                                                                  ##STR122##                 CH.sub.2                                                                           n.sub.D.sup.20 : 1.5579                 80                                                                                  ##STR123##                 CH.sub.2                                                                           m.p. 58° C.                      81                                                                                  ##STR124##                 CH.sub.2                                                                           n.sub.D.sup.20 : 1.5599                 82                                                                                  ##STR125##                 CH.sub.2                                                                           n.sub.D.sup.20 : 1.5830                 83                                                                                  ##STR126##                 CH.sub.2                                                                           m.p. 86° C.                      84                                                                                  ##STR127##                 CH.sub.2                                                                           m.p. 78° C.                      85                                                                                  ##STR128##                 CH.sub.2                                                                           m.p. 84° C.                      86                                                                                  ##STR129##                 CH.sub.2                                                                           n.sub.D.sup.20 : 1.5710                 87                                                                                  ##STR130##                 CH.sub.2                                                                           m.p. 86° C.                      88                                                                                  ##STR131##                 CH.sub.2                                                                           m.p. 76° C.                      89                                                                                  ##STR132##                 CH.sub.2                                                                           m.p. 84° C.                      90                                                                                  ##STR133##                 CH.sub.2                                                                           n.sub.D.sup.20 : 1.6059                 91                                                                                  ##STR134##                 CH.sub.2                                                                           n.sub.D.sup.20 : 1.5707                 92                                                                                  ##STR135##                 CH.sub.2                                                                           m.p. 60° C.                      93                                                                                  ##STR136##                 CH.sub.2                                                                           n.sub.D.sup.20 : 1.5162                 94                                                                                  ##STR137##                 CH.sub.2                                                                           m.p. 80° C.                      95                                                                                  ##STR138##                 CH.sub.2                                                                           n.sub.D.sup.20 : 1.5871                 96                                                                                  ##STR139##                 CH.sub.2                                                                           m.p. 72° C.                      97                                                                                  ##STR140##                 CH.sub.2                                                                           m.p. 110° C.                     98                                                                                  ##STR141##                 CH.sub.2                                                                           m.p. 74° C.                      99                                                                                  ##STR142##                 CH.sub.2                                                                           m.p. 196° C.                     100                                                                                 ##STR143##                 CH.sub.2                                                                           m.p. 130° C.                     101                                                                                 ##STR144##                 CH.sub.2                                                                           m.p. 80° C.                      102                                                                                 ##STR145##                 CH.sub.2                                                                           Fp.: 72° C.                      103                                                                                 ##STR146##                 CH.sub.2                                                                           Fp.: 68° C.                      104                                                                                 ##STR147##                 CH.sub.2                                                                           Fp.: 90° C.                      105                                                                                 ##STR148##                 CH.sub.2                                                                           Fp.: 120° C.                     106                                                                                 ##STR149##                 CH.sub.2                                                                           n.sub.D.sup.20 : 1.5396                 107                                                                                 ##STR150##                 CH.sub.2                                                                           Fp.: 104° C.                     108                                                                                 ##STR151##                 CH.sub.2                                                                           Fp.: 180° C.                     109                                                                                 ##STR152##                 CH.sub.2                                                                           Fp.: 94° C.                      110                                                                                 ##STR153##                 CH.sub.2                                                                           Fp.: 82° C.                      __________________________________________________________________________

USE EXAMPLES

In the use examples which follow the compound listed below was employedas comparison substance: ##STR154## methyl3-methoxy-2-(2-methylphenyl)-acrylate (disclosed in European Patent178,826).

EXAMPLE A Pyrenophora teres test (barley)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist.

After the spray coating has dried on, the plants are sprayed with aconidia suspension of Pyrenophora teres. The plants remain in anincubation cabin at 20° C. and 100% relative atmospheric humidity for 48hours.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 7 days after the inoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compounds of the following preparationexamples: 9, 10 and 12.

EXAMPLE B Erysiphe test (wheat)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with spores of Erysiphe graminisf.sp. tritici.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%, in order to promotethe development of mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compounds of the following preparationexamples: 1, 4, 5, 6, 8 and 11.

EXAMPLE C Erysiphe test (barley)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with spores of Erysiphe graminisf.sp. hordei.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%, in order to promotethe development of mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compounds of the following preparationexamples: 1, 4, 5, and 11.

EXAMPLE D Venturia test (apple)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous conidiasuspension of the apple scab causative organism (Venturia inaequalis)and then remain in an incubation cabin at 20° C. and 100% relativeatmospheric humidity for 1 day.

The plants are then placed in a greenhouse at 20° C. and a relativeatmospheric humidity of about 70%.

Evaluation is carried out 12 days after the inoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compounds of the following preparationexamples: 1 and 11.

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

We claim:
 1. A 2-methoximinocarboxylic ester of the formula ##STR155##in which Ar represents ##STR156## A represents --CH₂ --; ##STR157##where Y represents ##STR158## --SO₂ --CH₂ --; --O--; --CH═CH-- or --CH₂--CH₂ --,n represents the number 0 or 1, R represents alkyl,halogenoalkyl, alkenyl or halogenoalkenyl, or represents optionallysubstituted cycloalkyl, or and in the event that n is 0, may alsorepresent halogen, and X¹, X², X³ and X⁴ each independently representshydrogen, halogen, hydroxyl or methoxy, but in the event that X²represents bromine X³ does not simultaneously represent hydroxyl ormethoxy.
 2. A 2-methoximinocarboxylic ester according to claim 1, inwhichAr represents ##STR159## A represents one --CH₂ --; ##STR160##where Y represents ##STR161## --SO₂ --CH₂ --; --O--; --CH═CH-- or --CH₂--CH₂ --, n represents the number 0 or 1, R represents straight-chain orbranched alkyl having 1 to 8 carbon atoms, straight-chain or branchedhalogenoalkyl having 1 to 8 carbon atoms and 1 to 9 identical ordifferent halogen atoms, straight-chain or branched alkenyl having 2 to8 carbon atoms, straight-chain or branched halogenoalkenyl having 2 to 8carbon atoms and 1 to 9 identical or different halogen atoms, orrepresents cycloalkyl which has 3 to 7 carbon atoms and which isoptionally substituted by substituents independently selected from thegroup consisting of halogen and straight-chain or branched alkyl having1 to 6 carbon atoms, or R furthermore represents aryl which has 6 to 10carbon atoms and which is optionally substituted by substituentsindependently selected from the group consisting of halogen, cyano,nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio,alkylsulphinyl or alkylsulphonyl each of which has 1 to 6 carbon atoms,in each case straight-chain or branched alkenyl, alkynyl, alkenyloxy,alkynyloxy, alkenylthio or alkynylthio each of which has 2 to 6 carbonatoms, in each case straight-chain or branched halogenoalkyl,halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinyl andhalogenoalkylsulphonyl each of which has 1 to 6 carbon atoms and 1 to 13identical or different halogen atoms, in each case straight-chain orbranched halogenoalkenyl, halogenoalkynyl, halogenoalkenyloxy,halogenoalkynyloxy, halogenoalkenylthio or halogenoalkynylthio each ofwhich has 2 to 6 carbon atoms and 1 to 9 identical or different halogenatoms, in each case straight-chain or branched alkylcarbonyl,alkoxycarbonyl,alkylcarbonyloxy,alkylcarbonylamino,alkylcarbonyl(N-alkyl)-amimo,aminocarbonyl, N-alkyl-aminocarbonyl, N,N-dialkylaminocarbonyl oralkoximinoalkyl each of which has 1 to 6 carbon atoms in the individualalkyl moieties, and aryl, aryloxy, arylthio, arylcarbonyl,arylcarbonyloxy, arylcarbonylamino, arylcarbonyl(N-alkyl)amino,arylaminocarbonyl, N-aryl-N-alkylaminocarbonyl, arylalkyl or arylalkenyleach of which has 6 to 10 carbon atoms in the aryl moiety and up to 6carbon atoms in the individual alkyl or alkenyl moieties when presentand each of which is optionally substituted by substituentsindependently selected from the group consisting of halogen, cyano,nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio,alkylsulphinyl, or alkylsulphonyl each of which has 1 to 6 carbon atoms,in each case straight-chain or branched alkenyl, alkynyl, alkenyloxy,alkynyloxy, alkenylthio or alkynylthio each of which has 2 to 6 carbonatoms, in each case straight-chain or branched halogenoalkyl,halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinyl andhalogenoalkylsulphonyl each of which has 1 to 6 carbon atoms and 1 to 13identical or different halogen atoms, in each case straight-chain orbranched halogenoalkenyl, halogenoalkynyl, halogenoalkenyloxy,halogenoalkynyloxy, halogenoalkenylthio or halogenoalkynylthio each ofwhich has 2 to
 6. carbon atoms and 2 to 9 identical or different halogenatoms, in each case straight-chain or branched alkylcarbonyl,alkoxycarbonyl,alkylcarbonyloxy,alkylcarbonylamino,alkylcarbonyl(N-alkyl)-amino,aminocarbonyl, N-alkyl-aminocarbonyl, N,N-dialkylaminocarbonyl oralkoximinoalkyl each of which has 1 to 6 carbon atoms in the individualalkyl moieties, and aryl, aryloxy, arylthio, arylcarbonyl,arylcarbonyloxy,arylcarbonylamino,arylcarbonyl-(N-alkyl)amino,arylaminocarbonyl, N-aryl-N-alkylaminocarbonyl, arylalkyl or arylalkenyleach of which has 6 to 10 carbon atoms in the aryl moiety and up to 6carbon atoms in the individual alkyl or alkenyl moieties when presentand each of which is optionally substituted by substituentsindependently selected from the group consisting of halogen and in eachcase straight-chain or branched alkyl or alkoxy each of which has 1 to 6carbon atoms; and in the event that n is 0, R may also representfluorine, chlorine, bromine or iodine and X¹, X², X³ and X⁴ eachindependently represents hydrogen, fluorine, chlorine bromine, iodine,hydroxyl or methoxy, but in the event that X² represents bromine X³ doesnot simultaneously represent hydroxyl or methoxy.
 3. A2-methoximinocarboxylic ester according to claim 1, in whichArrepresents ##STR162## A represents --CH₂ --; ##STR163## where Yrepresents ##STR164## --SO₂ --CH₂ --; --O--; --CH═CH-- or --CH₂ --CH₂--, n represents the number 0 or 1, R represents straight-chain orbranched alkyl having 1 to 6 carbon atoms, straight-chain or branchedhalogenoalkyl having 1 to 6 carbon atoms and 1 to 9 identical ordifferent halogen atoms, straight-chain or branched alkenyl having 2 to6 carbon atoms, straight-chain or branched halogenoalkenyl having 2 to 6carbon atoms and 1 to 9 identical or different halogen atoms, cycloalkylwhich has 3 to 7 carbon atoms and which is optionally substituted bysubstituents independently selected from the group consisting ofstraight-chain or branched alkyl having 1 to 4 carbon atoms and halogen,or R represents aryl which has 6 or 10 carbon atoms and which isoptionally monosubstituted to pentasubstituted by substituentsindependently selected from the group consisting of fluorine, chlorine,bromine, cyano, nitro, in each case straight-chain or branched alkyl,alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl each of which has 1to 4 carbon atoms, in each case straight-chain or branched alkenyl,alkynyl, alkenyloxy, alkynyloxy, alkenylthio or alkynylthio each ofwhich has 2 to 4 carbon atoms, in each case straight-chain or branchedhalogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinyland halogenoalkylsulphonyl each of which has 1 to 4 carbon atoms and 1to 9 identical or different halogen atoms, in each case straight-chainor branched halogenoalkenyl, halogenoalkynyl, halogenoalkenyloxy,halogenoalkynyloxy, halogenoalkenylthio or halogenoalkynylthio each ofwhich has 2 to 4 carbon atoms and 1 to 7 identical or different halogenatoms, in each case straight-chain or branched alkylcarbonyl,alkoxycarbonyl, alkylcarbonyloxy, alkylcarbonylamino,alkylcarbonyl-(N-alkyl)-amino, aminocarbonyl, N-alkyl-aminocarbonyl,N,N-dialkylaminocarbonyl or alkoximinoalkyl each of which has 1 to 4carbon atoms in the individual alkyl moieties, and aryl, aryloxy,arylthio, arylcarbonyl, arylcarbonyloxy, arylcarbonylamino,arylcarbonyl(N-alkyl)amino, arylaminocarbonyl,N-aryl-N-alkylaminocarbonyl, arylalkyl or arylalkenyl each of which has6 to 10 carbon atoms in the aryl moiety and up to 4 carbon atoms in theindividual alkyl or alkenyl moieties when present and each of which isoptionally substituted by substituents independently selected from thegroup consisting of fluorine, chlorine, bromine, cyano, nitro, in eachcase straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulphinylor alkylsulphonyl each of which has 1 to 4 carbon atoms, in each casestraight-chain or branched alkenyl, alkynyl, alkenyloxy, alkinyloxy,alkenylthio or alkynylthio each of which has 2 to 4 carbon atoms, ineach case straight-chain or branched halogenoalkyl, halogenoalkoxy,halogenoalkylthio, halogenoalkylsulphinyl and halogenoalkylsulphonyleach of which has 1 to 4 carbon atoms and 1 to 9 identical or differenthalogen atoms, in each case straight-chain or branched halogenoalkenyl,halogenoalkynyl, halogenoalkenyloxy, halogenoalkynyloxy,halogenoalkenylthio or halogenoalkynylthio each of which has 2 to 4carbon atoms and 1 to 7 identical or different halogen atoms, in eachcase straight-chain or branched alkylcarbonyl, alkoxycarbonyl,alkylcarbonyloxy, alkylcarbonylamino, alkylcarbonyl-(N-alkyl)-amino,aminocarbonyl, N-alkyl-aminocarbonyl, N,N-dialkylaminocarbonyl oralkoximinoalkyl each of which has 1 to 4 carbon atoms in the individualalkyl moieties, and aryl, aryloxy, arylthio, arylcarbonyl,arylcarbonyloxy, arylcarbonylamino, arylcarbonyl-(N-alkyl)amino,arylaminocarbonyl, N-aryl-N-alkylaminocarbonyl, arylalkyl or arylalkenyleach of which has 6 to 10 carbon atoms in the aryl moiety and up to 4carbon atoms in the individual alkyl or alkenyl moieties when presentand each of which is optionally substituted by substituentsindependently selected from the group consisting of fluorine, chlorine,bromine and in each case straight-chain or branched alkyl or alkoxy eachof which has 1 to 4 carbon atoms; in the event that n is 0 R representchlorine or bromine X¹, X², X³ and X⁴ each independently representshydrogen, chlorine, bromine, hydroxyl or methoxy, but in the event thatX² represents bromine X³ does not simultaneously represent hydroxyl ormethoxy.
 4. A compound according to claim 1, wherein such compound ismethyl 3-[3-(4-chlorophenyl)-phenyl]-2-methoximinopropionate of theformula ##STR165##
 5. A compound according to claim 1, wherein suchcompound is methyl 3-(2-benzyloxyphenyl)-2-methoximinopropionate of theformula ##STR166##
 6. A compound according to claim 1, wherein suchcompound is methyl 3-(3-phenoxyphenyl)-2-methoximinopropionate of theformula ##STR167##
 7. A compound according to claim 1, wherein suchcompound is methyl 3-β-napthyl-2-methoximinopropionate of the formula##STR168##
 8. A compound according to claim 1, wherein such compound ismethyl 3-(3-biphenyl)-2-methoximinopropionate of the formula ##STR169##9. A fungicidal composition comprising a fungicidally effective amountof a compound according to claim 1 and a diluent.
 10. A method ofcombatting fungi which comprises applying to such fungi or to a locusfrom which it is desired to exclude such fungi a fungicidally effectiveamount of a compound according to claim
 1. 11. The method according toclaim 10, wherein such compound ismethyl3-[3-(4-chlorophenyl)-phenyl]-2-methoximinopropionate, methyl3-(2-benzyloxyphenyl)-2-methoximinopropionate, methyl3-(3-phenoxyphenyl)-2-methoximinopropionate, methyl3-β-napthyl-2-methoximinopropionate or methyl3-(3-biphenyl)-2-methoximinopropionate.